Wednesday, February 13, 2008

UNIT 13 HYDROGEN Position of hydrogen in periodic table, isotopes, preparation, properties and uses of hydrogen;----------------

Period 1 Group 1Atomic Number 1 Symbol H Atomic Weight 1.0079 Discovery Cavendish, 1766Hydrogen was prepared for many years before it was recognized as a distinct element. Electron Configuration 1s¹Word Origin Greek: hydro, water; genes, formingNamed by Lavoisier.

Hydrogen gas is so light and diffusive that uncombined hydrogen can escape from the atmosphere.

Hydrogen gas ordinarily is a mixture of two molecular forms, ortho- and para-hydrogen, which differ by the spins of their electrons and nuclei. Normal hydrogen at room temperature consists of 25% of the para form and 75% of the ortho form. The ortho form cannot be prepared in the pure state. Since the two forms of hydrogen differ in energy, their physical properties also differ.

Uses

Hydrogen is important in the proton-proton reaction and carbon-nitrogen cycle. Liquid hydrogen is used in cryogenics and in the study of superconductivity. Great quantities are used for the fixation of nitrogen from the air in the Haber ammonia process. Hydrogen is use in welding, for the hydrogenation of fats and oils, in methanol production, in hydrodealkylation, hydrocracking, and hydrodesulfurization. Other applications include producing rocket fuel, filling balloons, making fuel cells, producing hydrochloric acid, and reducing metallic ores. Deuterium is used as a moderator to slow down neutrons and as a tracer. Tritium is used in the production of the hydrogen (fusion) bomb. Tritium is also used in making luminous paints and as a tracer.

Sources

Hydrogen occurs in the free state in volcanic gases and some natural gases. Hydrogen is prepared by steam on heated carbon, decomposition of certain hydrocarbons with heat, action of sodium or potassium hydroxide on aluminum electrolysis of water, or displacement from acids by certain metals.

Heavy water is water that contains the heavy isotope of hydrogen called deuterium (chemical symbol D). The deuterium atom weighs about twice as much as ordinary hydrogen atom. Heavy water, also called deuterium oxide, makes up about 1 part in 5000 of ordinary water.

It was first separated from ordinary water in 1932 by G N Lewis, a chemist at the University of California.

Because of the difference between the weights of the two kinds of hydrogen atoms, the physical properties of heavy water differ from those of ordinary water. Heavy water freezes at 3.82oC and boils at 101.42oC.

Ice made from heavy water sinks in normal water.

Heavy water is useful in some kinds of nuclear reactors. It acts as a moderator to control the energy of the neutrons in a chain reaction. Seeds will not germinate in heavy water, and some animals, including tadpoles, cannot live in it.

Hydrogen peroxide, H2O2, was first discovered by Thenard among others in 1818 by reacting acids with barium peroxide, BaO2.

It resembles water in appearance being colourless in small quantities but blue when observed in thick layers.

It decomposes to oxygen and water and this decomposition is promoted by heat and alkalis.

Commercial grade H2O2 usually contains small amounts of stabilizers.

Hydrogen peroxide is a strong oxidising agent and is widely used as a bleaching agent. In dilute solutions it is an efficient antiseptic. The uses of hydrogen peroxide have been changing in recent years.

Hydrogen peroxide is produced by reducing alkylanthraquinone with hydrogen in the presence of a catalyst to the hydroquinone. After the catalyst has been removed to prevent decomposition of the hydrogen peroxide, the hydroquinone is oxidised, usually with air, back to quinone with a resultant co-production of hydrogen peroxide.

The hydrogen peroxide is removed and purified and the quinone is regenerated and returned to the reaction.

The anthraquinone must be dissolved in a suitable solvent for the hydrogenation, oxidation and extraction steps - this is usually referred to as the working solution. The solvent is usually a mixture because quinones dissolve readily in non-polar aromatic solvents, such as alkylbenzene, whereas hydroquinones dissolve well in polar solvents, such as alcohols and esters. A variety of different mixtures are in use but the aim is to satisfy a number of criteria, namely good solubility of both quinone and hydroquinone, good stability in both hydrogenator and oxidiser, low solubility in water and aqueous hydrogen peroxide solutions, sufficiently higher or lower density than water to ensure separation of the two phases during extraction, low volatility, high distribution coefficient for hydrogen peroxide in the solvent-water system and low toxicity. 1

In the hydrogenator, the working solution is reacted with hydrogen in the presence of a catalyst. The process is exothermic and the heat of reaction is removed by cooling the working solution before it enters the hydrogenator, by cooling the reactor during hydrogenation and/or by cooling the hydrogenated working solution.

After the hydrogenation reaction, the working solution must pass through a filtration stage to remove all traces of catalyst. Even small traces of catalyst in the oxidation and extraction stages lead to significant losses of hydrogen peroxide and could present safety problems. During the oxidation stage, air is passed through the hydrogenated working solution to convert the dissolved hydroquinones to quinones and form the hydrogen peroxide. The air outlet is passed over activated carbon adsorbers to recover solvent.

Crude hydrogen peroxide is extracted from the oxidised working solution by treating with water. The working solution is then regenerated and fed back to the front of the process and the crude hydrogen peroxide (15-35 wt%) is fed to a treatment unit where the concentration is increased to 50-70 wt%.